Fuel compositions with enhanced cold properties and methods of making the same

ABSTRACT

Methods of making a diesel fuel blend having enhanced cold properties; methods of lowering the cloud point of a mineral middle distillate fuel; and diesel fuel blends including a blend of a renewable fuel and a mineral middle distillate fuel.

FIELD OF THE INVENTION

The present invention relates to fuel compositions having enhanced coldproperties that are blends of mineral middle distillate fuels andrenewable fuels and methods for making such compositions.

BACKGROUND OF THE INVENTION

Sufficient cold temperature performance all year round is an essentialrequirement for diesel fuel. Due to large seasonal and geographictemperature variability, middle distillate fuels are blended andadjusted to minimize problems during cold weather such ascrystallization and solidification of the fuel which affects theviscosity of the fuel, its volatility, and its ability to pass throughfuel filters.

The most important properties of fuels related to their cold temperatureoperability are cloud point, pour point, and cold filter plugging point.As a middle distillate fuel is cooled, it will reach its cloud point.This is the temperature at which paraffin wax falls out of solution andstarts to form wax crystals in the fuel. The storage temperature of afuel is recommended to be higher than its cloud point. As the fuel isfurther cooled, it will eventually reach its pour point. This is thetemperature at which the fuel will no longer flow or the point at whichthe fuel gels or turns into a solid. The third important property of amiddle distillate fuel is its cold filter plugging point, which is thelowest temperature the fuel is filterable and can be used in vehicleswithout problems.

Because a component with poor cold properties will dominate in a blend,a fuel will be improved by adding components that have better coldproperties. The term “poor” or “poorer” refers to a higher temperaturevalue of cloud point or cold filter plugging point, and the term“better” refers to a lower temperature value of a cloud point or coldfilter plugging point.

Several approaches have been described to achieve transportation fuelsthat have good cold temperature operability. U.S. Pat. No. 9,006,501B2discloses a process for producing a renewable fuel blend, wherein abiologically derived feedstock is hydrotreated, and C14, C16, and C18normal paraffins (n-paraffins) are recovered from the hydrotreatedeffluent and blended with a renewable middle distillate. During thisprocess, n-paraffins are provided to the blend in quantities such thatthe blend does not require a pour point reducing treatment to achieve alow pour point. This process is complicated by requiring a step ofrecovering C14, C16, and C18 n-paraffins.

U.S. Patent Application Publication No. 2008/0163542 A1 discloses asynergistic fuel oil composition that enhances the cold temperatureoperability of the fuel. The composition comprises a petroleum-basedcomponent and a renewable fuel component. Biodiesel, ethanol, andbiomass are mentioned as examples of renewable fuel sources. Under ASTMD7467, however, only 6% to 20% biodiesel can be used in diesel equipmentwith no, or only minor, modifications.

It is also generally known that biodiesels, e.g., fatty acid methylesters (FAME), made by the trans-esterification process are inherentlymore sensitive to cold temperature operability compared to typicalpetroleum-derived fuels. In some cases fatty acid methyl esters cancause higher particle emissions and smoke development in a cold-drivenengine. The volume of fatty acid methyl esters allowed in diesel fuelsmay also be limited. European standards EN 16734 and EN 16709 specifythe requirements and test methods for diesel fuels that contain fattyacid methyl esters. According to EN 16734, B10 diesel fuel is dieselfuel that contains only up to 10 vol. % fatty acid methyl esters.According to EN 16709, high fatty acid methyl ester diesel fuels (B20and B30) contain only up to 20 vol. % or 30 vol. % fatty acid methylesters.

EP1664249B1 discloses fuel compositions prepared by blendingpetroleum-derived kerosene-based fuels and Fischer-Tropsch-derivedkerosene-based fuels. It discloses a finding that the freeze point ofsuch a blend is lower than the freeze points of both the blend'scomponents. The components used in these fuel compositions are notbio-based, however.

For the production of cold operable bio-based fuels, alternative fuelcompositions and blending methods are needed that are economical andhave no volume restrictions on the amount of bio-based fuel.

The cloud point of a fuel blend is a highly nonlinear combination of thecloud points of the original fuels. According to the state of the art, ablend will normally have a poorer cloud point than the weighted mean ofthe cloud points of its components. Therefore, while the cloud point ofa fuel may be improved by adding a component that has a remarkablybetter cold property, the use of this component will cause an increasein the cost of production.

There is therefore a need for a method of producing fuels by blendingcomponents in an economical way. In addition, there is a need for a fuelblend that has good cold properties and is less expensive to production.

BRIEF DESCRIPTION OF THE INVENTION

An object of the present invention is to provide a method and means toalleviate the disadvantages discussed above. The present inventionrelates to a method of making a diesel fuel blend having enhanced coldproperties; methods of lowering the cloud point of a mineral middledistillate fuel; and diesel fuel blends comprising a blend of arenewable fuel and a mineral middle distillate fuel. In addition, theinvention relates to the use of renewable fuel, typically a hydrotreatedrenewable middle distillate to enhance the cold properties of a fuelcomposition comprising mineral middle distillate.

The invention is based on studies that evaluated the cold properties ofmineral middle distillates, renewable fuels, and their blends. It wasdiscovered that a combination of a mineral middle distillate fuel with arenewable fuel resulted in an enhancement of the cloud point and coldfilter plugging point of the final blended fuel. It was also discoveredthat the cloud point and cold filter plugging point of certain blendswere lower than the linear blending assumptions estimated based on thecloud points of the fuels and lower than the cloud point or cold filterplugging point of both the blend's components.

More specifically the present diesel fuel blend may be described ascomprising a blend of a renewable fuel, such as hydrotreated renewablemiddle distillate, and a mineral middle distillate fuel in which therenewable fuel and mineral middle distillate fuel are present in a ratioof amounts by volume of from 10:90 to 90:10 and the diesel fuel blendcontains 10-25 wt % n-paraffins in the C14-C20 range and an amount ofisoparaffins in the C14-C20 range such that the ratio of the sum of wt %amounts of isoparaffins in the C14-C20 range to the sum of wt % amountsof n-paraffins in the C14-C20 range is less than 2.2. Experimentally ithas now been shown that the diesel fuel blend has a cloud point that islower than the weighted mean of the cloud points of the mineral middledistillate and the renewable fuel.

The synergistic effect described herein was surprising. Normally,blending results in a cloud point or cold filter plugging point that ishigher (i.e. poorer) than the value of each individual component. Thisincreases the costs of production because it is more expensive toproduce fuels that have better cold properties. But in the presentinvention, middle distillate production can utilize the blendingbehavior disclosed by using less expensive components with poorer cloudpoints to achieve the cloud point target.

Furthermore, in the present invention, the amount of renewable orbiocomponent in a fuel composition need not be limited to a maximum 7vol % by the EN 590:2013 standard as required for ester-type biodieselfuels, e.g., fatty acid methyl esters. Although higher amounts of fattyacid methyl esters may be considered, they require extra precautionsbecause they can affect fuel stability, cold properties, engine oildilution, and deposit formation in fuel injection systems.

The present invention shows that blending biocomponents into mineralmiddle distillate fuels is possible with renewable fuels such ashydrotreated renewable middle distillates to improve the coldtemperature operability of the blended fuel. This is shown in theexperimental part, where the measured cold properties of the blendedfuel were better than the weighted mean of the cold properties of itscomponents.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described in greater detail by means of preferredembodiments with reference to the attached accompanying drawings, inwhich

FIG. 1 shows the cloud point behavior in mineral diesel blends showingcalculated cloud points of blends as a line and measured values asdiamonds. The Y-axis is the cloud point (T; ° C.), and the X-axis is theincreasing percentage (vol-% of the total blend volume) of the mineraldiesel with poorer cloud point;

FIG. 2 shows the cloud points of the blend of Diesel 7 with Renewable Fand Renewable G showing calculated cloud points of blends as a line andmeasured values as diamonds for renewable F (cloud point −2° C.) and assquares for renewable G (cloud point −28° C.). The Y-axis is the cloudpoint (T; ° C.), and the X-axis is the increasing percentage (vol-% ofthe total blend volume) of the renewables;

FIG. 3 shows the cloud point behavior of a blend of a renewable fuelwith a cloud point of −28° C. and a mineral diesel with a cloud point of−5.5° C. The Y-axis is the cloud point (T; ° C.), and the X-axis is theratio (wt-% of the total paraffin content) of iso-paraffins ton-paraffins.

FIG. 4 shows the cloud point behavior of a blend of renewable fuel witha cloud point of −2° C. and a mineral diesel with a cloud point of −5.5°C. The Y-axis is the cloud point (T; ° C.), and the X-axis is the ratio(wt-% of the total paraffin content) of iso-paraffins to n-paraffins inthe C14-C20 range in said diesel fuel blend.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to fuel compositions, wherein enhancementof the cold properties of the final blended fuel composition is achievedby blending a mineral middle distillate component with a renewable fuelcomponent. The present invention further relates to a method of making adiesel fuel blend having enhanced cold properties; methods of loweringthe cloud point of a mineral middle distillate fuel; and diesel fuelblends comprising a blend of a renewable fuel component and a mineralmiddle distillate fuel component.

The term “cold properties” is used herein to refer to the cloud pointand cold filter plugging point of a fuel. The cloud point of a mineralmiddle distillate fuel is the temperature at which the heaviestn-paraffins are no longer soluble but precipitate out from the fuel,giving it a cloudy appearance. Cloud point conveys the lowest storagetemperature for the fuel to be usable and is one important parameter ina product's specification. Cloud point can be evaluated using, e.g., amethod defined in ASTM D2500, D5771, D5772, D5773, D7689, or EN 23015.The cold filter plugging point of a fuel is the temperature at and belowwhich wax in the fuel will cause severe restrictions when flowingthrough a filter. The cold filter plugging point is believed tocorrelate well with vehicle operability at lower temperatures. The coldfilter plugging point of petroleum fuels is typically evaluated usingASTM D6371 or EN 116. Both cloud point and cold filter plugging pointare measured and given as temperature (T, here ° C.).

The term “mineral” is used herein to denote components or compositionsthat are naturally occurring and derived from nonrenewable sources.Examples of such nonrenewable resources include petroleum oil or shaleoil and combinations thereof. The term “mineral” also refers to thewastes of nonrenewable sources.

Middle distillate is typically diesel fuel or kerosene. In the presentinvention, mineral middle distillate is preferably mineral diesel.Diesel fuel in general is any liquid fuel used in diesel engines, whosefuel ignition takes place, without spark, as a result of compression ofthe inlet air mixture and then the injection of fuel. The most commontype of diesel fuel is a specific fractional distillate of petroleumfuel oil. Distillation characteristics define how the fuel is evaporatedwhen it is sprayed into the combustion chamber of a diesel engine.Standards (e.g., EN590) include information about typical distillationcurves.

To distinguish from renewable diesel fuels not derived from petroleum,petroleum-derived diesel is referred to herein as “mineral diesel” or“mineral middle distillate”. It may also be called, e.g., petrodiesel,fossil diesel, or petroleum distillate. Mineral diesel can compriseatmospheric or vacuum distillates. The distillate can comprise crackedgas oil or a blend of any proportion of straight run or thermally orcatalytically cracked distillates. The distillate fuel can be subjectedto further processing such as hydrogen treatment or other processes toimprove fuel properties. Typically, mineral diesel comprises n- andisoparaffins at 10-70 weight %, naphtenics at 10-50 weight %,monoaromatics at 5-30 weight %, diaromatics at 0-10 weight %, and otheraromatics at 0-5 weight %.

In the present invention, a hydrotreated renewable middle distillatecomponent preferably comprises or consists of hydrotreated vegetableoil, hydrotreated animal fat, hydrotreated fish fat, hydrotreated fishoil, hydrotreated algae oil, hydrotreated microbial oil, hydrotreatedwood and/or other plant based oil, hydrotreated recyclable waste and/orresidue or a combination thereof. Preferably, the fresh feed ofrenewable fuel is selected from plant oils/fats, animal fats/oils, fishfats/oils, fats contained in plants bred by means of gene manipulation,recycled fats of food industry and combinations thereof. Hydrotreatingvegetable oils or animal fats is an alternative process toesterification for producing bio-based middle distillate fuels.Hydrotreated renewable middle distillate fuels are also referred to as“hydrotreated vegetable oil fuels”, “hydrotreated renewable diesels”,“renewable fuels”, “renewable diesels” or “renewable diesel components”instead of “biodiesel,” which is reserved for fatty acid methyl esters(FAME). Chemically hydrotreated renewable middle distillates aremixtures of paraffinic hydrocarbons and have very low quantities ofsulfur and aromatics. The cold properties of a hydrotreated renewablemiddle distillates can be adjusted to meet the local requirements byadjusting the amount of iso-paraffins by the severity of the process orby additional catalytic processing.

In the present invention, the isomerization ratio of the renewable fuel,such as hydrotreated renewable middle distillate is preferably at least50%, more preferably at least 60%. Isomerization ratios of more than 80%may be achieved, but has drawbacks, such as increase in resources neededduring the production. Preferably, the isomerization ratio of renewablefuel, such as hydrotreated renewable middle distillate is less than 69%,giving advantageous ranges from 50 to 69 and from 60 to 69%respectively. Higher isomerization ratio typically improves coldproperties but such a hydrotreated renewable middle distillate consumesmore resources during its production. The isomerization ratio means thetotal sum of iso-paraffins (weight %) divided by the total sum ofparaffins (weight %). Since hydrotreated renewable middle distillatesare hydrocarbons, they may be used as conventional middle distillatefuels. The fatty acid methyl ester specifications (EN 14214, ASTM D6751)do not apply for hydrotreated renewable middle distillates and thereforethere is no volume percent limitation on how much hydrotreated renewablemiddle distillates may be blended with diesel fuel.

Specifically, the present invention relates to a fuel composition whichcomprises a renewable fuel component that is blended with a mineralmiddle distillate component, which are the main components of thepresent diesel fuel blend. Certain amounts of iso-paraffins andn-paraffins in the range of C15 to C18 create blends having good coldproperties taking into account the resources used during the production.The invention relates to a diesel fuel blend comprising a blend of arenewable fuel and a mineral middle distillate fuel in which therenewable fuel and mineral middle distillate fuel are present in a ratioof amounts by volume of from 10:90 to 90:10 and the diesel fuel blendcontains 10-25 wt % n-paraffins in the C14-C20 range and an amount ofisoparaffins in the C14-C20 range such that the ratio of the sum of wt %amounts of isoparaffins in the C14-C20 range to the sum of wt % amountsof n-paraffins in the C14-C20 range is less than 2.2.

In one embodiment, the ratio of the sum of wt % amounts of isoparaffinsin the C14-C20 range to the sum of wt % amounts of n-paraffins in theC14-C20 range is from 1.1 to 2.2. This composition creates good coldproperties with low resource consumption during the production. Theweight percentages given here for paraffins refer to wt % of the totalblend fuel weight.

In one embodiment, in the composition, the amount of each C15-C18iso-paraffin is equal to or more than 2.2 weight % of the total mass ofthe fuel composition, and the amount of each C15-C18 n-paraffin is equalto or more than 1.9 weight % of the total mass of the fuel composition.This composition creates good cold properties with low resourceconsumption during the production.

Preferably, the amount of each C15-C18 n-paraffin is less than 10 weight% of the total mass of the fuel composition, more preferably less than9.6 weight %, and most preferably equal to or less than 7.9 weight %. Asreferred here, the C15-C18 paraffins are paraffins (straight chain orbranched alkanes) having a carbon number of 15, 16, 17, or 18. Thecarbon number denotes the number of carbon atoms in each paraffinmolecule. This composition creates good cold properties with lowresource consumption during the production.

In one embodiment, the amount of at least one C15-C18 iso-paraffin isequal to or more than 3.0 weight % of the total mass of the fuelcomposition, and the amount of at least one C15-C18 n-paraffin is equalto or more than 2.2 weight % of the total mass of the fuel composition.This composition creates good cold properties with low resourceconsumption during the production.

In one embodiment, a preferred fuel composition is obtained when thefollowing equation is satisfied for n-paraffins: the weight percentageof the n-paraffin in the range of C16 to C18 with the smallest weightpercent subtracted from the weight percentage of the n-paraffin in therange of C16 to C18 with the largest weight percent divided by theweight percentage of the n-paraffin in the range of C16 to C18 with thelargest weight percent, is equal to or more than 0.26 and preferablyequal to or less than 0.45. In another embodiment, the amounts ofn-paraffins C16 and C17 fulfill the equation 0.26<(C16-C17)/C16<0.45.This composition creates good cold properties with low resourceconsumption during the production.

In one embodiment, a preferred fuel composition is obtained when thefollowing equation is satisfied for iso-paraffins: the weight percentageof the iso-paraffin in the range of C15 to C18 with the smallest weightpercent subtracted from the weight percentage of the iso-paraffin amountin the range of C15 to C18 with the largest weight percent divided bythe weight percentage of the iso-paraffin in the range of C15 to C18,with the largest weight percent is equal to or more than 0.49 andpreferably equal to or less than 0.63. In another embodiment, theamounts of iso-paraffin carbon numbers C15 and C18 fulfill the equation0.49<(C18-C15)/C18<0.63. This composition creates good cold propertieswith low resource consumption during the production.

In one embodiment, the difference between the cloud point and/or coldfilter plugging point of the renewable fuel component and the mineralmiddle distillate component is equal to or less than 17° C., and morepreferably, the difference is between 0 and 13.1° C. This differencecreates good cold properties with low resource consumption during theproduction. Generally, the cloud point and cold filter plugging point inthe blend is lower than the calculated (weighted mean) cloud points. Thecold properties in the renewable fuel component may be better than thecold properties in the mineral middle distillate component. In the sameway, the mineral middle distillate component may have better coldproperties than the renewable fuel component in the blend.

The fuel composition may be a hydrocarbon fuel composition that may alsocontain generally used additives. The sum volume of the renewable fueland the mineral middle distillate components is typically at least 98%,preferably at least 99% and most preferably at least 99.9% of the totalblend fuel volume, the rest being generally used additives. The mineralmiddle distillate component may comprise more than one mineralcomponent, and the renewable fuel component may comprise more than onerenewable component. Preferably, the renewable fuel component ishydrotreated renewable middle distillate, and the mineral middledistillate component is mineral diesel.

According to a specific embodiment, the sum volume of the renewable fueland the mineral middle distillate components is at least 90 vol %,preferably at least 93 vol %, This kind of blend may contain othercomponents compatible with diesel engines, such as fatty acid methylesters (FAME) up to 10 vol %, preferably up to 7 vol %. This compositioncreates good cold properties with low resource consumption during theproduction and allows the use of broader variety of components in blend.

The fuel can contain about 100% renewable fuel; however, in the presentinvention, the renewable fuel and mineral middle distillate componentsare blended in a volume percent ratio less than 100% (renewable:mineralmiddle distillate; 100:0). Preferably, the renewable fuel and mineralmiddle distillate components are blended in a volume percent ratio ofless than 90:10 (renewable fuel: mineral middle distillate). In oneembodiment, the renewable fuel and mineral middle distillate componentsare blended in a volume percent ratio of 20:80 to 80:20 (renewable fuel:mineral middle distillate). This composition creates good coldproperties with low resource consumption during the production. Inanother embodiment, the renewable fuel and mineral middle distillatecomponents are blended in a volume percent ratio of 20:80 to 60:40. Thiscomposition creates even better cold properties with low resourceconsumption during the production.

In another embodiment, the diesel fuel blend has isoparaffins in theC14-C20 range from 22 wt % to 55 wt % of the total blend fuel weight.This creates good cold properties with low resource consumption duringthe production.

The invention further relates to the use of hydrotreated renewable fuelsfor enhancing the cold properties of a fuel composition containingmineral middle distillate. The hydrotreated renewable fuel content in amineral middle distillate blend can be determined by 14C isotopemethods, which enable one skilled in the art to distinguish betweenfossil and renewable carbon. The principles of this method can be foundin the standard ASTM D6866.

Any blend fuel as described above, may be produced by a method, which isnext described. Herein is thus provided a method of making a diesel fuelblend having enhanced cold properties comprising selecting a renewablefuel and a mineral middle distillate fuel having cloud points thatdiffer by no more than 17° C., preferably by no more than 13° C.; andblending the renewable fuel and mineral middle distillate fuel in aratio of amounts by volume of from 10:90 to 90:10 to form a diesel fuelblend, wherein the diesel fuel blend contains 10-25 wt % n-paraffins inthe C14-C20 range and an amount of isoparaffins in the C14-C20 rangesuch that the ratio of the sum of wt % amounts of isoparaffins in theC14-C20 range to the sum of wt % amounts of n-paraffins in the C14-C20range is less than 2.2, preferably from 1.1 to 2.2; and the diesel fuelblend has a cloud point that is lower than the weighted mean of thecloud points of the mineral middle distillate and the renewable fuel.

In one embodiment, is provided a method of use for lowering the cloudpoint of a mineral middle distillate fuel comprising: determining thecloud point of a mineral middle distillate fuel; selecting a renewablefuel having a cloud point that differs by no more than 17° C.,preferably by no more than 13° C. from the cloud point of the mineralmiddle distillate fuel; and blending the renewable fuel and mineralmiddle distillate fuel in a ratio of amounts by volume of from 10:90 to90:10 to form a diesel fuel blend having a cloud point that is lowerthan the cloud point of the mineral middle distillate fuel, wherein thediesel fuel blend contains 10-25 wt % n-paraffins in the C14-C20 rangeand an amount of isoparaffins in the C14-C20 range such that the ratioof the sum of wt % amounts of isoparaffins in the C14-C20 range to thesum of wt % amounts of n-paraffins in the C14-C20 range is less than 2.2to form a diesel fuel blend having a cloud point that is lower than thecloud point of the mineral middle distillate.

In one embodiment, the invention relates to a method of use for loweringthe cloud point of a mineral middle distillate fuel comprising:determining the cloud point of a mineral middle distillate fuel;selecting a renewable fuel having the following properties: (i) a cloudpoint that differs by no more than 17° C., preferably by no more than13° C. from the cloud point of the mineral middle distillate fuel; (ii)an amount of n-paraffins sufficient to provide a diesel fuel blendcontaining 10-25 wt % n-paraffins in the C14-C20 range when therenewable fuel is blended with the mineral middle distillate fuel; and(iii) an amount of isoparaffins in the C14-C20 range sufficient toprovide a diesel fuel blend having a ratio of the sum of wt % amounts ofisoparaffins in the C14-C20 range to the sum of wt % amounts ofn-paraffins in the C14-C20 range of from 1.1 to 2.2 when the renewablefuel is blended with the mineral middle distillate fuel; and blendingthe renewable fuel with the mineral middle distillate fuel in a ratio ofamounts by volume of from 20:80 to 80:20 to form a diesel fuel blendhaving a cloud point that is lower than the cloud point of the mineralmiddle distillate.

In one embodiment, the invention relates to a method of use for loweringthe cloud point of a renewable fuel comprising: determining the cloudpoint of a renewable fuel; selecting a mineral middle distillate fuelhaving a cloud point that differs by no more than 17° C., preferably byno more than 13° C., from the cloud point of the renewable fuel; andblending the renewable fuel and mineral middle distillate fuel in aratio of amounts by volume of from 10:90 to 90:10 to form a diesel fuelblend having a cloud point that is lower than the cloud point of arenewable fuel, wherein the diesel fuel blend contains 10-25 wt %n-paraffins in the C14-C20 range and an amount of isoparaffins in theC14-C20 range such that the ratio of the sum of wt % amounts ofisoparaffins in the C14-C20 range to the sum of wt % amounts ofn-paraffins in the C14-C20 range is less than 2.2, preferably from 1.1to 2.2, to form a diesel fuel blend having a cloud point that is lowerthan the cloud point of the renewable fuel.

A diesel fuel blend obtainable by a method or use as described above,has been experimentally shown to have enhanced cold properties inrelation to components thereto.

EXAMPLES

The following examples are provided to better illustrate the claimedinvention and are not to be interpreted as limiting the scope of theinvention. To the extent that specific materials are mentioned, it ismerely for purposes of illustration and is not intended to limit theinvention. One skilled in the art may develop equivalent means orreactants without the exercise of inventive capacity and withoutdeparting from the scope of the invention. It will be understood thatmany variations can be made in the procedures described herein whilestill remaining within the bounds of the present invention. It is theintention of the inventors that such variations be included within thescope of the invention. The weight percentages given in relation toparaffins refer to wt % of the total blend fuel weight. The volumepercentages given in relation to fuel components refer to vol % of thetotal blend fuel volume.

Comparative Example 1

To lower the cloud point of a mineral middle distillate (fossil fuelcomponent) having a cloud point of −5.5° C. by −0.5 to −6° C. it isnecessary to add to the fossil fuel component a second fuel componentwith a lower cloud point. Typically, when two or more fuel componentswith different cloud points are blended together the final blend has ahigher cloud point than what would be expected based on the weightedmean value of the cloud points of the components. When 20 vol % of arenewable fuel component (Renewable G) with a cloud point of −28° C. wasblended with the fossil component which has a cloud point of −5.5° C., acloud point of 6.6° C. was achieved. The difference in cloud pointbetween this renewable fuel component and the fossil fuel component wasgreater than 17° C., making it a comparative example. The weightpercentages of n-paraffins of the blended fuels were measured by gaschromatography and are shown in Table 1 below.

In the blend, the total wt-% of n-paraffins C14, C15, C16, C17, C18,C19, and C20 was 9.18%, the total wt-% of iso-paraffins C14, C15, C16,C17, C18, C19, and C20 was 26.09% and the ratio ofn-paraffins/iso-paraffins in blend was 2.84. The cloud point of theblend could be lowered even further when the amount of renewable fuelwith the −28° C. cloud point was increased to 40 vol-%, 60 vol-% and 80vol-% in the blend. The cloud points of the resulting blends at variousvolume percentages are shown in FIG. 2. FIG. 3 shows the relationshipbetween cloud point and paraffin ratio for the blends. For all ratios ofrenewable fuel to fossil fuel, however, the cloud points of the blendswere higher than calculated by the weighted mean value of cloud pointsof the components (FIG. 2). This was as predicted according to currentpractice.

The weight percentages of n-paraffins in the fuel components beforeblending were measured by gas chromatography and are shown in Table 1.The weight percentages of n-paraffins in the blended fuel compositionswere measured by gas chromatography (Table 2). The weight percentages ofiso-paraffins in the fuels to be blended were measured by gaschromatography (Table 3). The weight percentages of iso-paraffins in theblended fuel compositions were measured (Table 4). In theabove-mentioned blends, the cumulative sums of n-paraffins C14, C15,C16, C17, C18, C19, and C20 were 9.18-7.78 wt-%, the cumulative sums ofiso-paraffins C14, C15, C16, C17, C18, C19, and C20 were 26.09-72.46wt-% and the ratios of the cumulative sum of iso-paraffins C14, C15,C16, C17, C18, C19, and C20 and the cumulative sum of n-paraffins C14,C15, C16, C17, C18, C19, and C20 were 2.84-9.31 wt-%.

Example 1

When 20 vol % of a renewable fuel (Renewable F) which has a cloud pointof −2° C. was blended with 80 vol % of a fossil component which has acloud point of −5.5° C., a lower cloud point than the cloud point ofeither component was achieved. This synergist effect is achieved whenthe ratio of the cumulative sum of iso-paraffins C14, C15, C16, C17,C18, C19, and C20 and the cumulative sum of n-paraffins C14, C15, C16,C17, C18, C19, and C20 in the blend was 1.6. The cumulative sum ofn-paraffins C14, C15, C16, C17, C18, C19, and C20 in the blend was 13.6wt-%. The cumulative sum of iso-paraffins C14, C15, C16, C17, C18, C19,and C20 in the blend was 21.87 wt-%.

Example 2

When 40 vol % of a renewable fuel (Renewable F) which has a cloud pointof −2° C. was blended with 60 vol % of a fossil component which has acloud point of −5.5° C., a lower cloud point than the cloud point ofeither component was achieved. This synergist effect is achieved whenthe ratio of the cumulative sum of iso-paraffins C14, C15, C16, C17,C18, C19, and C20 and the cumulative sum of n-paraffins C14, C15, C16,C17, C18, C19, and C20 in the blend was 1.9. The cumulative sum ofn-paraffins C14, C15, C16, C17, C18, C19, and C20 in the blend was 17.6wt-%. The cumulative sum of iso-paraffins C14, C15, C16, C17, C18, C19,and C20 in the blend was 33.11 wt-%.

Example 3

When 60 vol % of a renewable fuel (Renewable F) which has a cloud pointof −2° C. was blended with 40 vol % of a fossil component which has acloud point of −5.5° C., a lower cloud point than the cloud point ofeither component was achieved. This synergist effect is achieved whenthe ratio of the cumulative sum of iso-paraffins C14, C15, C16, C17,C18, C19, and C20 and the cumulative sum of n-paraffins C14, C15, C16,C17, C18, C19, and C20 in the blend was 2.05. The cumulative sum ofn-paraffins C14, C15, C16, C17, C18, C19, and C20 in the blend was 21.55wt-%. The cumulative sum of iso-paraffins C14, C15, C16, C17, C18, C19,and C20 in the blend was 44.4 wt-%.

Example 4

When 80 vol-% of a renewable fuel (Renewable F) which has a cloud pointof −2° C. was blended with 20 vol % a fossil component which has a cloudpoint of −5.5° C., a lower cloud point than the cloud point of eithercomponent was achieved. This synergist effect is achieved when the ratioof the cumulative sum of iso-paraffins C14, C15, C16, C17, C18, C19, andC20 and the cumulative sum of n-paraffins C14, C15, C16, C17, C18, C19,and C20 in the blend was 2.18. The cumulative sum of n-paraffins C14,C15, C16, C17, C18, C19, and C20 in the blend was 25.5 wt-%. Thecumulative sum of iso-paraffins C14, C15, C16, C17, C18, C19, and C20 inthe blend was 55.6 wt-%.

The following tables report the data from Comparative Example 1 andExamples I-4. The weight percentages of n-paraffins in the fuels to beblended were measured by gas chromatography and are shown in Table 1.The weight percentages of n-paraffins in the blended fuel compositionswere measured by gas chromatography (Table 2). The weight percentages ofiso-paraffins in the fuels to be blended were measured by gaschromatography (Table 3). The weight percentages of iso-paraffins in theblended fuel compositions were measured (Table 4).

TABLE 1 The weight % of n-paraffins of the fuel components. Carbonnumber n-paraffin Renewable F Renewable G 14 0.41 0.26 15 5.49 1.75 169.57 2.21 17 5.09 1.65 18 8.83 1.44 19 0.05 0.02 20 0.06 0.01

TABLE 2 The weight % of n-paraffins in the blended fuel compositions.Carbon 20% 20% 40% 40% 60% 60% 80% 80% number Renew. Renew. Renew.Renew. Renew. Renew. Renew. Renew. n-paraffin F G F G F G F G 14 1.151.12 0.97 0.91 0.78 0.69 0.59 0.47 15 2.31 1.57 3.11 1.61 3.90 1.66 4.691.70 16 3.01 1.54 4.65 1.70 6.29 1.87 7.93 2.04 17 2.23 1.54 2.94 1.573.66 1.60 4.38 1.62 18 2.79 1.31 4.30 1.34 5.81 1.37 7.32 1.41 19 1.121.12 0.86 0.84 0.59 0.57 0.32 0.29 20 0.99 0.98 0.76 0.74 0.52 0.49 0.290.25

TABLE 3 The weight % of iso-paraffins of the fuel components. Carbonnumber iso-paraffin Renewable F Renewable G 14 0.82 1.69 15 8.64 15.0716 18.83 24.92 17 14.21 20.70 18 23.80 24.97 19 0.28 0.32 20 0.26 0.24

TABLE 4 The weight % of iso-paraffins in the blended fuel compositions.Carbon 20% 20% 40% 40% 60% 60% 80% 80% number Renew. Renew. Renew.Renew. Renew. Renew. Renew. Renew. i-paraffin F G F G F G F G 14 1.551.72 1.37 1.71 1.19 1.70 1.00 1.69 15 2.95 4.24 4.37 6.95 5.80 9.65 7.2212.36 16 4.89 6.10 8.37 10.81 11.86 15.51 15.34 20.22 17 4.08 5.38 6.619.21 9.14 13.04 11.68 16.87 18 5.75 5.99 10.27 10.73 14.78 15.48 19.2920.23 19 1.52 1.53 1.21 1.23 0.90 0.93 0.59 0.63 20 1.13 1.13 0.91 0.900.70 0.68 0.48 0.46

In these examples the composition of the fossil component was such thatthe cumulative sum of iso-paraffins C14, C15, C16, C17, C18, C19, andC20 was 10.63 wt-%, the cumulative sum of iso-paraffins C8, C9, C10,C11, C12, and C13 was 6.45 wt-%, the cumulative sum of iso-paraffinsC21, C22, C23, C24, C25, and C26 was 3.13 wt-%, the cumulative sum ofn-paraffins C14, C15, C16, C17, C18, C19, and C20 was 9.63 wt-%, thecumulative sum of 4-paraffins C8, C9, C10, C11, C12, and C13 was 3.84wt-%, the cumulative sum of n-paraffins C21, C22, C23, C24, C25, and C26was 2.58 wt-%.

Comparative Example 2

When 20 vol-%, 40 vol-%, 60 vol-% and 80 vol-% of a renewable fuelcomponent with a cloud point −35° C. was blended with a fossil fuelcomponent with a cloud point of 5.5° C., all cloud points of the blendswere higher than calculated by weighted mean value of cloud points ofcomponents. This was as predicted according to current practice. In theabove-mentioned blends, the cumulative sums of n-paraffins C14, C15,C16, C17, C18, C19, and C20 were 8.41-4.50 wt-%. The cumulative sums ofiso-paraffins C14, C15, C16, C17, C18, C19, and C20 were 26.25-76.25wt-%. The ratios of the cumulative sum of iso-paraffins C14, C15, C16,C17, C18, C19, and C20 and the cumulative sum of n-paraffins C14, C15,C16, C17, C18, C19, and C20 were 3.1-17.0. The weight percentages ofiso- and n-paraffins in the blended fuel compositions were measured bygas chromatography.

Comparative Example 3

When 20 vol-%, 40 vol-%, 60 vol-% and 80 vol-% of a renewable dieselfuel component with a cloud point −27° C. was blended with a fossil fuelcomponent with a cloud point of −5.5° C., all cloud points of the blendswere higher than calculated by weighted mean value of cloud points ofcomponents. This was as predicted according to current practice. In theabove-mentioned blends, the cumulative sums of n-paraffins C14, C15,C16, C17, C18, C19, and C20 were 9.16-7.70 wt-%, the cumulative sums ofiso-paraffins C14, C15, C16, C17, C18, C19, and C20 were 26.00-75.22wt-% and the ratios of the cumulative sum of iso-paraffins C14, C15,C16, C17, C18, C19, and C20 and the cumulative sum of n-paraffins C14,C15, C16, C17, C18, C19, and C20 were 2.6-6.8. The weight percentages ofiso- and n-paraffins in the blended fuel compositions were measured bygas chromatography.

Comparative Example 4

When 20 vol-%, 40 vol-%, 60 vol-% and 80 vol-% of a renewable dieselfuel component with a cloud point −23° C. was blended to with a fossilfuel component with a cloud point of −5.5° C., all cloud points of theblends were higher than calculated by weighted mean value of cloudpoints of components. This was as predicted according to currentpractice. In the above-mentioned blends, the cumulative sums ofn-paraffins C14, C15, C16, C17, C18, C19, and C20 were 9.61-9.53 wt-%,the cumulative sums of iso-paraffins C14, C15, C16, C17, C18, C19, andC20 were 25.66-73.76 wt-% and the ratios of the cumulative sum ofiso-paraffins C14, C15, C16, C17, C18, C19, and C20 and the cumulativesum of n-paraffins C14, C15, C16, C17, C18, C19, and C20 were 2.7-7.7.The weight percentages of iso- and n-paraffins in the blended fuelcompositions were measured by gas chromatography.

Comparative Example 5

Two mineral diesel blends having different cloud points were blended.The cloud points of the blends were measured by a method defined in EN23015 and EN 116. Measured cloud point values for mineral diesel blendsare presented in Table 5 and FIG. 1, respectively. The calculated linearvalues in Table 5 are based on linear behavior, which means a weightedmean of cloud points of the components. The linear behavior is averageof the cloud points and it is in other words accomplished by weightingthe cloud points of components by the volume percent of components inthe blend. Analysis shows that the poorer cloud point componentdominates.

TABLE 5 Cloud points of mineral diesel blends. Volume percent Volumepercent Cloud point (%) of Diesel (%) of Diesel Cloud point of blend °C. with cloud with cloud of blend ° C. (calculated point −27.8° C. point−4.3° C. % (measured) linear) 80% 20% −18.8 −23.1 60% 40% −13.3 −18.440% 60% −9.5 −13.7 20% 80% −6.4 −9.0

FIG. 1 shows that components with poorer cloud point values dominated inthe mineral diesel blends. The term “poorer” means a higher temperaturevalue of a cloud point or cold filter plugging point, and the term“better” means a lower temperature value of a cloud point or cold filterplugging point.

Example 5

Renewable hydrotreated vegetable oil compositions with different coldproperties were blended with mineral diesel in different volumes. Thecloud points and/or cold filter plugging points of the blends weremeasured by methods defined in EN 23015 and EN 116 and are shown inTable 6. It can be seen that the blending produced lower, i.e., better,measured cloud points and cold filter plugging points than expected bycalculating a weighted mean of cloud points of the components. In somecases, the blend had even better cold properties than the coldproperties of its individual components. Measured cloud points were evenmore than 3° C. better compared to the calculated weighted mean of coldproperties. Also, the cold filter plugging points were better in blendsthan in neat mineral fuel.

TABLE 6 Cloud points and cold filter plugging points of mineral dieseland renewable hydrotreated vegetable oil diesel blends. Cold filter Coldfilter Cloud point Cloud point, plugging point, plugging pointdifference of ° C. ° C. Cloud point weighted mean, components,(measured) (measured) weighted mean ° C. ° C. Renewable A 6.5 4 Diesel 1−4.3 −6 20% Renewable −5.5 −8 −2.1 −4 10.8 A + 80% Diesel 1 Diesel 2−5.1 −6 20% Renewable −6.1 −9 −2.8 −4 11.6 A + 80% Diesel 2 Diesel 3−3.8 −5 20% Renewable −4.8 −7 −1.7 −3.2 10.3 A + 80% Diesel 3 RenewableB −2.0 −5 Diesel 1 −4.3 −6 20% Renewable −5.6 −9 −3.8 −5.8 2.3 B + 80%Diesel 1 Diesel 2 −5.1 −6 20% Renewable −6.3 −8 −4.5 −5.8 3.1 B + 80%Diesel 2 Diesel 3 −3.8 −5 20% Renewable −5.0 −7 −3.4 −5 1.8 B + 80%Diesel 3 Renewable C −1.1 −4 Diesel 2 −5.1 −6 20% Renewable −6.4 −8 −4.3−5.6 4 C + 80% Diesel 2 Renewable D −15.3 −15 Diesel 4 −28.0 −29 20%Renewable −28.5 −36 −25.5 −26.2 12.7 D + 80% Diesel 4 40% Renewable−26.3 −27 −22.9 −23.4 12.7 D + 60% Diesel 4 50% Renewable −24.8 −24−21.7 −22 12.7 D + 50% Diesel 4 60% Renewable −22.5 −23 −20.4 −20.6 12.7D + 40% Diesel 4 80% Renewable −19.1 −19 −17.8 −17.8 12.7 D + 20% Diesel4 Diesel 5 −28.4 −28 20% Renewable −26.8 −29 −25.8 −25.4 13.1 D + 80%Diesel 5 Diesel 5 −28.4 −28 50% Renewable −23.4 −23 −21.9 −21.5 13.1 D +50% Diesel 5 Renewable H −9.8 −12 Diesel 8 −3.9 −15 80% Renewable −11.8−8.6 5.9 H + 20% Diesel 8 60% Renewable −10.9 −7.4 5.9 H + 40% Diesel 840% Renewable −8.1 −7.0 5.9 H + 60% Diesel 8 20% Renewable −5.7 −5.1 5.9H + 80% Diesel 8

In contrast to the cloud point value, the cold filter plugging pointvalue can be improved by cold flow improver additives, which aretypically polyethylenevinylacetates, i.e., poly-EVAs. Other typicaladditives are lubricity improvers and electricity conductive improvers.Diesel 6 and Diesel 8 include cold flow improvers.

Example 6

Seven percent fatty acid methyl ester was added to the 100% renewablehydrotreated vegetable oil diesel (Renewable E) or its blend withmineral diesel (Diesel 6). The cloud points and the calculated cloudpoint weighted mean of the Diesel 6 and Renewable E blend with theaddition of fatty acid methyl ester were measured.

TABLE 7 The cloud points and the calculated cloud point weighted mean ofthe mineral diesel (Diesel 6) and renewable hydrotreated vegetable oildiesel (Renewable E) blend with the addition of fatty acid methyl ester.Weighted Cloud point Cloud mean of difference of point, cloud point offossil and ° C. Diesel 6 and renewable diesel (measured) Renewable Ecomponents,° C. Renewable E −10 Diesel 6 −5 80% Renewable E + −11.8 −9 520% Diesel 6 60% Renewable E + −10.9 −8 5 40% Diesel 6 7% fatty acidmethyl −9 −10 5 ester and 93% Renewable E + 0% Diesel 6 7% fatty acidmethyl −10.8 −9 5 ester and 93% blend of 80% Renewable E + 20% Diesel 67% fatty acid methyl −10.5 −8 5 ester and 93% blend of 60% Renewable E +40% Diesel 6

In Example 7, the cloud point difference between Diesel 6 and RenewableE is 5° C. Results show that fatty acid methyl ester as a blendingcomponent causes poorer cloud point, but blending according to presentinvention can alleviate this effect. Hence, according to one embodimentof the present invention, blending up to 7 vol-% fatty acid methylester, with blend fuel of renewable fuel and mineral middle distillateaccording to claim 1, the cloud point, which is lower than the weightedmean of its components, can be achieved. Said cloud point may even belower than that of any individual component.

It will be apparent to a person skilled in the art that, as thetechnology advances, the inventive concept can be implemented in variousways. The subject matter in the above described embodiments may becombined in any permutations or manner. The same applies to subjectmatter of all dependent claims which may be used in any combination torestrict the independent claims. The invention and its embodiments arenot limited to the examples described above but may vary within thescope of the claims.

1-19. (canceled)
 20. A method of making a diesel fuel blend havingenhanced cold properties, the method comprising: selecting a renewablefuel component and a mineral middle distillate fuel component havingcloud points that differ by no more than a pre-selected temperaturevalue; and blending the selected renewable fuel component and theselected mineral middle distillate fuel component in a ratio of amountsby volume of from 10:90 to 90:10 to form a diesel fuel blend thatcomprises 10-25 wt % n-paraffins in a C14-C20 range and an amount ofiso-paraffins in a C14-C20 range such that a ratio of a sum of wt %amounts of the iso-paraffins in the C14-C20 range to a sum of wt %amounts of the n-paraffins in the C14-C20 range is less than 2.2 or isfrom 1.1 to 2.2.
 21. The method of claim 20, wherein the blending isperformed so that the ratio of the sum of wt % amounts of theiso-paraffins in the C14-C20 range to the sum of wt % amounts of then-paraffins in the C14-C20 range is less than 2.2 and is also greaterthan or equal to 1.1.
 22. The method of claim 20, wherein the renewablefuel component is a hydrotreated renewable middle distillate component.23. The method of claim 22, wherein the hydrotreated renewable middledistillate component comprises one or more of: a hydrotreated vegetableoil, a hydrotreated animal fat, a hydrotreated fish fat, a hydrotreatedfish oil, a hydrotreated algae oil, a hydrotreated microbial oil, ahydrotreated wood, a hydrotreated plant based oil, a hydrotreatedrecyclable waste, and a hydrotreated recyclable residue.
 24. The methodof claim 22, wherein the hydrotreated renewable middle distillatecomponent has an isomerization ratio of at least 50% or at least 60%.25. The method of claim 22, wherein the hydrotreated renewable middledistillate component has an isomerization ratio of from 50% to 69%. 26.The method of claim 20, wherein the selected renewable fuel componentand the selected mineral middle distillate fuel component are blended ina ratio of amounts by volume of from 20:80 to 80:20.
 27. The method ofclaim 20, wherein the pre-selected temperature value is 1.8° C., 2.3°C., 3.1° C., 3.5° C., 4° C., 5° C., 10.3° C., 10.8° C., 11.6° C., 12.7°C., 13° C., 13.1° C., or 17° C.
 28. A diesel fuel blend comprising: arenewable fuel component and a mineral middle distillate fuel componentin which the renewable fuel component and mineral middle distillate fuelcomponent are present in the diesel fuel blend in a ratio of amounts byvolume of from 10:90 to 90:10; and the diesel fuel blend of therenewable fuel component and the mineral middle distillate fuelcomponent having 10-25 wt % n-paraffins in a C14-C20 range and an amountof iso-paraffins in the C14-C20 range, such that a ratio of a sum of wt% amounts of the iso-paraffins in the C14-C20 range to a sum of wt %amounts of the n-paraffins in the C14-C20 range is less than 2.2 or isfrom 1.1 to 2.2.
 29. The diesel fuel blend of claim 28, wherein theratio of the sum of wt % amounts of the iso-paraffins in the C14-C20range to the sum of wt % amounts of the n-paraffins in the C14-C20 rangeis less than 2.2 and greater than or equal to 1.1.
 30. The diesel fuelblend of claim 28, wherein the renewable fuel component is ahydrotreated renewable middle distillate component.
 31. The diesel fuelblend of claim 30, wherein the diesel fuel blend also includes fattyacid methyl esters (FAME).
 32. The diesel fuel blend of claim 31,wherein a sum volume of the hydrotreated renewable middle distillatecomponent and the mineral middle distillate component in the diesel fuelblend is an amount that is at least 90 vol % and the diesel fuel blendalso includes fatty acid methyl esters (FAME) in an amount that is up to10 vol % of the diesel fuel blend.
 33. The diesel fuel blend of claim31, wherein a sum volume of the hydrotreated renewable middle distillateand the mineral middle distillate component in the diesel fuel blend isan amount that is at least 93 vol % of the diesel fuel blend and thediesel fuel blend also includes fatty acid methyl esters (FAME) in anamount that is up to 7 vol % of the diesel fuel blend.
 34. The dieselfuel blend of claim 30, wherein the hydrotreated renewable middledistillate component comprises one or more of: a hydrotreated vegetableoil, a hydrotreated animal fat, a hydrotreated fish fat, a hydrotreatedfish oil, a hydrotreated algae oil, a hydrotreated microbial oil, ahydrotreated wood, a hydrotreated plant based oil, a hydrotreatedrecyclable waste, and a hydrotreated recyclable residue.
 35. The dieselfuel blend of claim 28, wherein the renewable fuel component and themineral middle distillate fuel component are present in the diesel fuelblend in a ratio of amounts by volume of from 20:80 to 80:20.
 36. Thediesel fuel blend of claim 30, wherein the hydrotreated renewable middledistillate component and the mineral middle distillate fuel componentare present in the diesel fuel blend in a ratio of amounts by volume offrom 20:80 to 80:20.
 37. The diesel fuel blend of claim 30, wherein thediesel fuel blend includes the hydrotreated renewable middle distillatecomponent between 10 vol % and 20 vol % of a volume of the diesel fuelblend.
 38. The diesel fuel blend of claim 30, wherein the hydrotreatedrenewable middle distillate component includes a mixture of paraffinichydrocarbons.
 39. A fuel blend comprising: a renewable fuel componentand a mineral middle distillate fuel component in which the renewablefuel component and mineral middle distillate fuel component are presentin the fuel blend in a ratio of amounts by volume of from 10:90 to90:10; and the fuel blend of the renewable fuel component and themineral middle distillate fuel component having 10-25 wt % n-paraffinsin a C14-C20 range and an amount of iso-paraffins in the C14-C20 range,such that a ratio of a sum of wt % amounts of the iso-paraffins in theC14-C20 range to a sum of wt % amounts of the n-paraffins in the C14-C20range is less than 2.2 or is from 1.1 to 2.2.